Azo dyes and method for their preparation



Patented May 14, 1935 This invention more particularly AZO DYES 1 PREPAR Miles Augustinus Dahlen,-,

signor to E. I. du Pont' Del., a corporation of Delpany, Wilmington, aware"" 7N0 Drawing. Application March so, 1933,

Serial .No.

ATION Wilmington; DeL, asde Nemours,& Com- 'l'z'o'lsim H (or 26077) Y i ner with the meta-nitranilide of 2,3-hydroxyto new azo dyes-and water insoluble disazo relates refers to dyes having the following'general formula:

in which A represents ameta-arvlene nucleusof thebenzene sents an arylene. thalene, diphenyl component.

or naphthalene series X repre,- nucleus of the benzene, naphor diphenyl-ether series, and

R represents the residue of an ice color coupling It is "an object of the, present invention to prepare insoluble azo the fiber.

which are well adapted for use in one-bath dyeing processes.

to prepare dyes A still further object is to produce bright attractive dyes which impart shades of satisfactory fastness to textile fibers whenprepared thereon. Additional from a considerati'on'of the fol become apparent lowing description.

objects will These objects are attained according to the herein described invention wherein aromatic diamineshaving'the following general formula:

NH2-ANHCO-X CONH ANH2 A and X have th given.

trat ive examples,

stated in parts by 1 Cottonskeins, ,i

are tetrazotized and coupled with an ice colorcoupling component.

In this formula the terms e same me weight:

Erarnple -l; I H mpregnated in;the usual manat the boil, rinse prepared as follows:

naphthoic acid, were developed in a tetrazo bath prepared as followsz;

was filtered and the withjsodium acetate.

I When the development of the color in the above bath was complete, the skeins were rinsed, soaped d and dried.

By this process abright red-scarlet dyestufi of the probable structure:

t NHQOOoONH E I 'NOa is-obtaine d. :V'I'he color possesses fair fastness to light and washing.

Example 2 Cotton skeins, impregnated in the usual manher with the meta-nitranilide of 2,3-hydroxynaphthdic acid, were developed in a tetrazo bath prepared,

NHCO- Example 3 v Cotton skeins, impregnated in the usual manner with the alpha-naphthalide of 2,3-hydroxynaphthoic acid, were developed in a tetrazo bath 18.7. 1 parts- H of N,N-di-(4-methyl 3 amino phenyD-terephthalamide were stirred ini '30 parts ofhydrochloric acid of 30%" strength and,

O F CE] before.

fastness to light and goodfastness to washing acetate;

350 parts of cold water, and the base tetrazotized with '7 parts of sodium nitrite dissolved in 30 parts of water. When tetrazotization was complete, the solution was filtered and the mineral acidi n ut al ed hsqd um ace at When the development of pthe'dyestufi was complete, the skeins were soape'd and rinsed as By this process a red dyestufi of iair was obtained. The dye'stufi has the probable formula:

on H; 1 -o ONE-j Z Example J 4.

Co on ske ns; padded in t e i s wil mann r with the alpha-naphthalide Y of 2,3-hydroxynaphthoic acidwere developed in-a tetrazo bath prepared as follows:

20.3 parts of N,N-di-(2-rnethoxy-5-aminophenyl) -terephthalamide were stirred in parts of hydrochloric acid of 36% strength and 350 parts 'of cold Water, and the base tetrazotized with-'1 partsof sodium nitrite dissolved in 30; parts or water. The tetrazo solution was filtere and the mineral acidity neutralized with sodium After the development the rinsing and soaping of the slceins, a red Borde dyeing i fair. fatns s o. if sht. and waste a obt n ,T. e roba ly possesse he fol w ormula: V

V NirooOcoNH C to k in l fpaddefd: with the parachloranilide of; 2,-.3 -hydroxy=uaphthoicacid; were developed in a tetrazq bath prepared asiollowsr in the above bath, and

the; usual manner phenyl) -terephthalamide were stirred in 30 parts of hydrochloric acid of 30%strength and 350 parts of cold water, and the base tetrazotized with '7 parts of sodium nitrite dissolved in 30 parts of water. The tetrazo solution was filtered and the mineral acidity neutralized with sodium acetate.

After the development in the above bath, and the rinsing and soaping of the skeins, a scarletred dyeing of good fastness to washing was obtained. The dye probably possesses the following formula:

sumo-O0 ONH A solution of the anilide o! 2,3-hydroxy-naphthoic acid was prepared by stirring 10 parts of. the anilide with 5 parts of alcohol, adding 25 parts of sodium hydroxide or 25% strength and 500 parts of water. A tetrazo solution prepared from N,N' -di- (2-methoxy-5-aminophenyl) -terephthalamide was prepared as in Example 4. An equivalent quantity of the tetrazo solution was added to the solution of the anilide, resulting in coupling to form the insoluble pigment possessing the followin constitution: V i

Mac 000 oNHf docs, onto The pigment was filtered, washed and dried. It formed a violet powder, which dissolved in concentrated sulfuric acid to a bluisheviolet solution.

, 7 Example 7 v 1a): ms or N,N-d l-(4 -methyl-3 aminophe- 'nyl) terephthalamide,were, stirred in1 30 parts of hydrochloric acid of"3 Q% strength and 350 parts of cold water, and the base tetrazotized by the. additionot '1 parts of sodium nitrite dis-"- solved in 30 parts of water. When tetrazotization was complete, the solution was filtered. 18 parts of the sodium salt of piperidine-alpha-carboxylic acid were then added, followed by sufficient sodiurn carbonate solution to render the mass strong- ,ly alkaline to Brilliant Yellow papers. When interaction to form the diazoimino compound was complete, as shown by a negative test for tetraz o salt, the mass was saturated with sodium chloride. cipitated was separated and dried at a low tem- 'perature. It was a tan solid which was 'very soluble in water and alkalies, and has the probable formula:

A printing powder was preparedby the mechanical mixture of equal parts of the above diazoimino compound and .the alpha-naphthalide of 2,3-hydroxy-naphthoic acid. A printing paste was then made up according to the following formula:

13 parts of the printing powder 3 parts of Turkey red oil g r 5 parts of caustic soda'of 30% strength 67 parts of starch tragacanth thickener 12 parts of water heated to 160 F.

Cotton piece goods were printed from an engraved copper roll with theiabove paste. The printed fabric was then subjected to the action of live steam containing the vapors of acetic acid, at a temperature of about 212 F. Rapid development of the pattern to a deepred 0f ood fastness properties was thus effected. The goods were soaped, rinsed and dried. The dyestuff was identical in formula with that obtained according to Example 3.

It is readily apparent that other secondary amines containing water solubilizing groups may be used in preparing the diazoimino compound suitable for usein the above andrelated printing processes. Following is alist, of a few representative amines which maybe substituted for piperidine-alpha-carboxylic acid:

' OHaNHCHnCOOH v -'sarcosine CHQOHaNHCHzCHzSOINB. ethyl-taurine GHQ-OH: "ljl'OlinB H: rr-ooon omomcnoroionmnom methyI-gmcamine" It is, of course, to be understood that the components of the aforementioned examples are merely'a few of the many which come'within the terms of the present invention and which maybe used with very satisfactory results.

thalene series. This nucleus may be further substituted by alkyl, alkoxy; halogen and other groups having similar effects, but should be free from groups which render the resulting dyestuffs water soluble, such as carboxylic and sulfonic acid groups.

I The'component designated by'Xisanar ylene nucleus of thejbenzene, naphthaleneidiphenyl or diphenyl ether series. This component like- The diazoimino compound thus pre-v For exam- V ple, the component heretofore designated by A is a meta-arylene nucleus ofthe' benzene or naphwise "may be further substituted; for instance by Hydroxy-anthracene-carboxylic acids Hydroxy-diarylamine-carboxylic acids Alkyl-aminoand aryl-amino 2 7 hydroxynaphthalene-3-carboxylic acids Likewise, other ice color coupling components such as acylacetyl derivatives of varylamines and arylene diamines, alphaand beta-naphthol, alpha-naphthol substituted in the 4-position by acyl groups, aryl-alkyl-pyrazolones, and dihydroxy-quinolines, fall within the scope of this in-. vention andmay be used with'good results.

The diamines which are tetrazotized to form the diazo salts described herein may be obtained may be mentioned the following: 1 a

A meta-.nitro-arylamine of the formula:

is condensed with an arylene-dicarbonyl-chloride of the formula:

by various .well known methods, among-which ClCO-X-COC1 This results in the formation of a dinitro compound having the following general formula:

which compound upon reduction according to Well known methods, such as by the action of iron and an acid or by liquid phase hydrogenation over suitable catalysts, is converted to the. dijamino compoundpreviously referred to.

In carrying out the synthesis of these diamines an exceedingly wide range of compounds may be used, resulting in the production of numerous and attractive shadesin the finished products. For instance, representative 'meta-nitro-arylamin'es selected from the large group which are suitable.

for use in the preparation of the new diamines used in the present invention are:

Meta-nitraniline 3-Nitro 4-chloro-aniline 4-Nitro-2-amino-toluene 4-Nitro-2-amino-anisole 6-Nitro-4-amino-1-3-dimethyl-benzene 2-Nitro-4-amino-toluene 2-Nitro-4-amino-anisole 2-Chloro-4-amino-6-nitro-toluene 3-Nitro-I-naphthylamine I Y 1-Chloro-2-amino-4-nitro-naphthalene Representative arylene .dicarbonyl chlorides selected from among those which maybe used for this'arylamideiaryl- 0 ephthalamide lene-1,4-dioarbonylamide in producing thenew diamines comprised ,within the scope of the present invention are;

0rtho-, riieta and para-benzene-dicarbonylchlorides 2-Methyl-benz'ene-1,4-dicarbonyl chloride- 4 2-Chloro-benzene-l,4-dicarbonyl-ch1orides I 2-Methoxy-benz;ene#:1;4;-dicarbonyl-chloride Naphthalene -1,4;dicarbonyhchloride Naphthalene-1,8-dicarbonyl-chloride Diphenyl-AA'-dicarbonylchloride Diphenyl-2,2-dicarbonyl-chloride Diphenyl-ether-xlA'-dicarbonyl-chloride Concerning the resulting diamines, mention may be made of the following which are of particular interest in the manufacture of the new dyestuffs:

N,N -di (2,4-dimethyl 5 a ino phen n terephthalamide i V N,N' di (2 ,5-dieth0xy 3 amino phenyl) ter- N,N- di -I(;2- ethyl-5-methoxy 3-,- amino -phenyl) -phthalamidel N,N-di (3 amino phenyl) diphenyl 4,4 dicarbonylamide N,N' -di- (3-amino-6-methyl-pheny1) -naphtha- N,N -di- (3-amino-naphthyl) met a -phthalamide . nitranilides, tolidides,

, developed with N,N'.' di (3-amino-6-methoxy phenyl) i diphenyl-ether-4,4-dicarbonylamide.

In the selection of the ice color coupling. components, aspreviously mentioned there is' an almostequally wide range from which to choose. In the selection" of these components the arylamides of 2,3-hydr0xy' naphthoic acid arezpreferred; -Amongthe: most satisfactory of these arylamides reference may be made to the anilides, toluidides, anisidides, 'phenetidides, naphthalides,

dianisidides, the 4;'-carboxanilido-anilides, and other derivatives produced by substituting non-water solubilizing groups,

v,nitro amino, alkoxy, ala such as halogen; alkyl, kylamino, and arylamino The dyes described groups thereon.

mixtures of the water the much older method wherein theflbers are impregnated with the coupling componentand the diazo salt. li'urthermore, the products may be produced in substance and-used as pigments As is quite apparent from a consideration of thepreceding description, the choice of components is exceptionally largeancl results 1 in the production of a wide variety of very desirable colors. t v

As many apparently widely; different embodiments of this invention may be made without departing from the spirit and scope-thereof, it is to do not limit myself tothe specific embodiments thereof except asi deflned I be understood that I in the appended claims,

I claim: i 1

which comprises tetrazotizing and coupling a diamine having the following general formula:

herein are readily applied by the one-bath method of dyeing, wherein soluble diazoimino derivatives of the tetrazotized diamino compounds with a the group consisting: of ss fi xltev ssne we? me eiths' swam in; which A represents, a meta-arylene nucleus f the benzene-or naphthalene series and" XI represents arylenenucleus of the: benze'njeinaphm l wiphe y urrent-e h series, wi an ice color'eouplingfcomponent. j

2. The process of elaiml l [wherein the nuclei representedjby A x'may have substituted thereon members selected from .the c ass" {onsistm al e a ko e h l u s- 3. A process for making insoluble azo'i dyes which comprises-tetrazbtizing and coupling a diaminehaving the following general formula; I I mi A-mnco -x -conm-A nm v in which A represents a meta-aryl'ene nucleus of lected from the -group consisting 'of amino-benv zenes" and amino-naphthalenes, -which amines may have substituted thereon members'selected from the group consisting of, a1kyl,aa1koxy, halogenandnitro. 1

5. A process for making dyes which comprises" tetrazotizing and coupl'in'gl adiamine having the following generalformula: i

NH2ANHCO-X.--CONH -ANH2 in which A represents a meta-arylene nucleus of ,1

the benzene series and X represents an arylene nucleus of the benzene se'ries; with an arylamide o1 2,3-hydroxy-naphthoicacid.

6. A process for making imsoluble azo dyes which comprises tetrazotizing and coupling adiamine having the following general formula:'

in which I represented hydrogen, halogen,=a1kyl or alkoxy group, with an ary-lamidel "drox'y-naphthoic acid derived from an selected from the group consistingof amino-benzenes and aminonaphthalenes.

- 7. Insoluble azo dyes having the following gen- I R R an arylenelnucleus 'o'f th'e' benzene, naphthalene,

of the benzene or naphthalene series, which may have substituted thereon members selected. from alkyl, alkoxy and halo- 3 wherein the nuclei I have substituted thereon members selected from the group con of 2,3-hywherein the 'arylamide is diphenyl or, diphenyleether series, and R, repre- I sents'thez radical of'an'ice color coupling compo- 1. A process for making insoluble azo dyes which A represents meta'aryl-ene nucleus zene, naphthalene, diphenyl or diphenyl-ether series, which may have substituted thereon members selected from the group consisting of alkyl, alkoxy and halogen, and R represents the radical of an ice color coupling component.

9. Insoluble azo dyes having the following general formula:

N=NANHCOXCONHAN=N i t in which A represents a meta-arylene nucleus of the benzene or naphthalene series, X represents an arylene nucleus of the benzene, naphthalene, diphenyl or diphenyl-ether series, and R represents the radical of an arylamide of 2,3-hydroxy-naphthoic acid.

10. Insoluble azo dyes general formula:

1 I=N-A-NHoo-X-ooNHA-N=1 -I R R in which A represents a meta-arylene nucleus having the following of the benzene or naphthalene series, which may have substituted thereon members selected from the group consisting of alkyl, alkoxy and halogen, X represents an arylene nucleus of the benzene, naphthalene, diphenyl or diphenyl-ether in which A represents a meta-arylene nucleus of the benzene series, X represents an arylene nucleus of the benzene series and R represents the radical of an arylamide of 2,3-hydroxynaphthoic acid.

12. Insoluble azo dyes having the following general formula:

Y Y N=N A -N=N OH 111110 o-l- -'OONH no ONE-R1 V Ri -BNO ois which R1 represents an aromatic radical of the benzene or naphthalene series, and Y represents a hydrogen, halogen, alkyl or alkoxy group. c MILES AUGUSTINUS DAHLEN.

consisting of alkyl, al-- 

